Lijun Yang,Jiaxing Zhang,Mengfan Wang,Yutong Wang,Wei Qi,Zhimin He
As bridging species between short peptides and macromolecular proteins, peptide assemblies not only provide a supramolecular approach for the fabrication of controllable molecular machines with enzyme-like functions, but also a simplified model for understanding the catalytic mechanism of natural enzymes. In this study, we focused on probing the effect of microenvironment on the catalytic behavior of peptide assemblies. Upon simply replacing the X residue in Fmoc-FFXAH-CONH 2 , we realized the modulation of the microenvironment of the amyloid assemblies, which thus appeared esterase-like function with different catalytic abilities. The chemistry , structure and activity were analyzed to explore the principles that how the hydrophobic, charged, polar and chiral microenvironment deciding the catalytic behavior of the esterase mimic. In addition, we also presented the potential of the catalytic assemblies in the encapsulation, delivery and enzymatic metabolization of a mutual prodrug . This work sheds new insights for understanding the structure–function relationship of catalytic peptide assemblies and natural enzymes, and also provides a new avenue for the designing of artificial enzymes with better functions.
Self-assembled Eu-dipeptide (tryptophan-phenylalanine) microparticles with multi-emission fluorescence was prepared and modified with a single-stranded DNA corresponding to the sulfamethazine (SMZ) adapter (Eu-PMPs@cDNA). Aptamer-functionalized magnetic Fe 3 O 4 (MNPs@aptamer) was used to specifically bind the target SMZ. Using Eu-PMPs@cDNA as fluorescent signal probe and MNPs@aptamer as catcher, a noncompetitive fluorescence sensing strategy was developed for determination of SMZ with good sensitivity, accuracy, selectivity, and stability. Under the optimized conditions, fluorescence increases linearly in the 0–20 ng/mL SMZ concentration range, and the detection limit is 0.014 ng/mL. The fluorescence sensing method was applied to analysis of water and fish muscle samples, and recoveries ranged from 81.78 to 119.46 % with relative standard deviations below 4.2 %. This study offered a reliable and sensitive fluorescence sensing strategy for SMZ determination in food samples, which owns great potential for wide-ranging application in harmful compounds assay by simply changing the type of aptamer and its complementary single-stranded DNA.